AU689045B2

AU689045B2 - Cement treated with high-pressure CO2

Info

Publication number: AU689045B2
Application number: AU59835/96A
Authority: AU
Inventors: Roger H. Jones Jr.
Original assignee: Materials Technology Ltd
Current assignee: Materials Technology Ltd
Priority date: 1995-06-07
Filing date: 1996-06-03
Publication date: 1998-03-19
Anticipated expiration: 2016-06-03
Also published as: WO1996040601A1; EP0840713A4; CN1187179A; CN1046690C; AR002371A1; EA000302B1; EP0840713A1; JPH10511073A; MX9709700A; EG20663A; IL118370A; JP3261384B2; US5518540A; PE11297A1; EA199800010A1; TW331555B; IL118370A0; CA2224065C; KR100252841B1; AU5983596A

Description

WO 96/40601 PCT/US96/08848 1 CEMENT TREATED WITH HIGH-PRESSURE CO 2 BACKGROUND OF THE INVENTION This invention relates to improving characteristics of cement by subjecting it to dense-phase gaseous (very high pressure) or supercritical (fluid) carbon dioxide (C0 2 to alter the morphology and/or chemistry of hardened portland, lime or pozzolanic cement paste and permit manipulation of its properties and behavior. The invention further relates to testing cement to determine the extent to which additives in the cement may resist the carbonation of the cement.

As disclosed in my copending, commonly owned U.S.

patent application (Serial No. 08/390,468, filed January 27, 1995, for Cement Mixtures With Alkali-Intolerant Matter and Method of Making Same), the disclosure of which is incorporated herein and made part hereof by reference, cement carbonation may be used to neutralize alkalinity to permit incorporation of alkali-intolerant materials into the wet paste to make superior products. That application discloses to expose cement to low-pressure carbon dioxide.

Cement carbonation, wherein naturally-occurring carbon dioxide in the atmosphere gradually combines with the calcium hydroxide in the cement matrix to form calcium carbonate and water, is generally considered undesirable because concrete containing steel reinforcement relies upon high alkalinity to inhibit steel corrosion. As carbonation takes place over time, alkali is reduced and the prophylaxis the steel receives against corrosion is lessened. Eventually, the steel begins to corrode, thereby weakening the concrete.

The stoichiometry of the carbonation reaction is: Ca(OH) 2

+CO

2 CaCO 2

H

2 0 In contrast, deliberate carbonation to purposely reduce hydroxide using gaseous CO 2 as is disclosed in my abovereferenced patent application, quickly and completely V WO 96/40601 PCTflS96/08848 2 eliminates the alkalinity in hardened cement pastes, whether the paste is acting alone or as part of other materials such as concretes or composites. The only morphological change that is visibly apparent under scanning electron microscope (SEM) examination is the absence of ettringite and portlandite and the appearance of visible micro-crystals of calcite (often called "dog teeth") in what prior to carbonation was calciumsilicate-hydrate gel. Some change is noted in the micromorphology, but pores and capillaries are still discernible and relatively plentiful. I have discovered that a much greater visible change takes place when dense-phase or supercritical carbon dioxide is infused. The diversity of structures is reduced and a regular "rice-grain" morphology is now evident. Another change that is clearly apparent in both cases using powder X-ray diffraction (XRD) is that the portlandite and ettringite peaks are absent in the spectrographic signature. They have been replaced by a very strong calcite peak. An identical chemical change can be observed in powder XRD of cement pastes carbonated by means of supercritical CO 2 As noted above, during experimentation it was discovered that when a cement matrix is exposed to carbon dioxide in its supercritical state, massive, observable morphological changes occur. The result is a densified, simplified microstructure with fewer different types of crystals, and exhibiting fewer micro-pores and microcapillaries than is typical of cements carbonated by means of relatively low-pressure gaseous CO 2 or cements which have not been deliberately carbonated at all. The flat, plate-like structures indicative of portlandite, and the fine, needlelike crystals of ettringite are absent. In their place are rounded, closely packed, siliceous crystals with a "rice grain" appearance, neatly aligned with one another and with few or no visible pores or capillaries.

It was further discovered that supercritical C0 2 long recognized as a polar solvent, can, if desired, simultaneously be used to infuse the hardened cement matrix with materials dissolved or suspended in the supercritical CO 2

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WO 96/40601 PCTIUS96/08848 3 to alter the properties and behavior of the hardened cement.

In addition, because certain cement whose original wet mixes contained methyl cellulose polymer as an additive refused to carbonate, even when exposed to the extreme pressures and concentrations of CO2 in its supercritical state, the very process of forcing supercritical carbon dioxide into the matrix enabled one to determine to what extent a cement would ultimately carbonate, if it would do so at all. It also became evident that the methyl cellulose prevented cement carbonation since it was the only material not present in the other mix designs tested.

Finally, it was discovered that other materials with matrices similar to cement, particularly ceramics whose pore structure and density can be easily controlled during formulation and firing, can also be infused with materials transported by the supercritical C02.

The advantages and results obtained with the present invention as discussed below are attainable with supercritical CO2, as above defined, and dense-phase CO 2 Both of them readily flow into and through cement (unless specially treated to close its passages), particularly under the high pressure of supercritical C02.

CO

2 becomes supercritical when it reaches a temperature of at least 310C and a pressure of at least 1071 psi. Further, supercritical CO2 retains its supercritical characteristics even if, thereafter, its temperature drops below the supercritical threshold so long as at least the threshold pressure is maintained. Dense-phase C02 is not supercritical and does not simultaneously behave like a liquid and a gas because it has not reached a temperature of 31 0 C and a pressure of 1071 psi. Dense-phase C02 is highly compressed gas; say of a pressure of 80 to 100 atmospheres or more but which has never reached a temperature of at least 31 0 C so that it does not have the characteristics typical of supercritical C02. For purposes of the present invention, dense-phase CO2 behaves similar to supercritical CO with the exception that dense-phase C0 2 unlike supercritical C02, does not dissolve or suspend certain materials soluable or suspendable in I A- WO 96/40601 PCTIUS96/08848 4 supercritical CO 2 as is discussed below. Thus, unless otherwise stated, "supercritical CO 2 as used herein, including the claims, is intended to and does collectively refer to supercritical CO 2 and dense-phase CO 2 except in those instances, including the claims, which address the solubility or suspendability of certain materials in supercritical CO 2 when the term "supercritical C0 2 1 excludes "dense-phase C02" SUMMARY OF THE INVENTION When a material is used as a reinforcement and/or aggregate in cement mixes made with portland, lime, pozzolanic or other appropriate hydraulic cement, the strength and flexibility contributed by such reinforcement and/or aggregate is in direct proportion to the strength of the bond between it and the cement matrix. To increase compressive or flexural strength, it is therefore necessary to increase the tenacity of the bond. Cement zarbonation integrates the aggregate or reinforcing glass, plastic, natural materials or blends or materials into the matrix of the cement by forming a structurally sound, unimpaired bond between the cement and the reinforcement and/or aggregate. It does this by reducing or eliminating the portlandite in the transition phase surrounding these materials and by filling voids in the cement with tightly packed crystals of calcium carbonate.

Consequently, the strength is greater than is possible when using alkali-tolerant, coated glass or the relatively weaker, alkali-tolerant plastics.

The present invention therefore uses cement which has been carbonated to convert its pH to neutral as a binder for glass and/or certain plastic, naturally occurring aggregates, fibers, cloth and/or roving as a substitute for alkali-resistant glass and plastics; for example, to make such products as fiberglass reinforced cement board and many others.

Thus, it is an object of the present invention to use supercritical CO 2 to densify and simplify the matrices of hardened hydraulic cement pastes, including cement pastes formulated completely or in part with portland cement, self-

I

0 .4 WO 96/40601 PCT/US96/08848 cementing or alkali-activated fly-ash pozzolans, natural pozzolans, alkali-activated or self-cementing slags or lime and possibly containing other additives, reinforcements or aggregates.

It is a further purpose of this invention to use supercritical CO 2 to determine if a hardened hydraulic cement will resist carbonation.

A still further purpose of this invention is to use supercritical Co 2 (which in accordance with the earlier definition of this term now excludes dense-phase C0 2 to transport dissolved or certain suspended organic and/or inorganic materials into the pores and capillaries of hardened and fully hydrated cement matrices to thereby alter physical and/or chemical properties and the behavior of cement matrices.

Another purpose of this invention is to utilize supercritical CO 2 to carbonate ceramic or hardened hydraulic cement matrices, reducing alkalinity to approximately pH 7, while simultaneously densifying and simplifying the morphology of the microstructure and infusing other materials dissolved, and under certain circumstances suspended in the CO 2 An additional purpose of this invention is to use supercritical CO 2 to infuse conductive materials into cement matrices to alter the electrical properties and behavior of the latter.

It is a further purpose of this invention to use supercritical CO 2 to infuse materials into cement matrices which, at conditions of elevated temperatures, will melt or otherwise fuse or combine with the materials and structures of the cement matrix to impart altered physical, electrical or mechanical properties, or other desirable behavior and properties.

It is a still further object of this invention to use supercritical CO 2 to infuse hardened hydraulic cement matrices with dissolved substances that will react when subsequently exposed to certain other chemicals and solvents.

Another objective of this invention is to use supercritical CO 2 to infuse the matrices with substances that WO 96/40601 PCT/US96/08848 6 will prevent disruptive reaction resulting from subsequent exposure to chemicals and solvents.

DESCRIPTION OF THE PREFERRED EMBODIMENTS This invention contemplates to employ manufacturing processes similar to those currently utilized to produce products shaped of rigid thermoplastics, metals or ceramics.

These processes include the molding of articles, their extrusion and pultrusion, as well as casting, sintering, machining or forging, as is discussed in more detail below.

Molded products, particularly rigid thermoplastics and ceramics, are formed in numerous ways. Among these are injection molding and rotational molding, which have the common characteristic that a plastic material is forced into a mold made of one or more parts in the shape of the desired finished product. Once the material is placed in the mold, it is allowed or caused to harden and the mold is then opened to release the finished article. In accordance with the present invention, hydraulic cement is forced into the mold. For purposes of this specification, "hydraulic cement" is meant to and does include any or all of a mixture of portland, pozzolan or lime, and such cement may include additives to provide increased strength, color, hardening speed or other desired characteristics. These additives may further include such materials as fibrous'reinforcements, aggregates, catalytic chemicals or plasticizers.

Another means of forming plastics and metals into products is by extrusion, in which the plastic material is forced through an orifice that gives rise to the shape of the finished product, or by pultrusion, in which the plastic material is drawn or pulled, rather than pushed, through a forming orifice.

In casting processes, a liquefied material is simply poured into a mold where it cures or hardens into a product having the shape of the mold and from which it is later removed by parting the mold. This echnique is commonly used to form ceramics and metals. Metals may also be beaten into shape in the forging process.

-II I WO 96140601 PCTIUS96/08848 7 Finally, plastics, metals and some ceramics may be machined into their final forms using rotary lathes and milling devices.

All of these techniques are suitable for forming products from materials made in accordance with the present invention.

A typical process in accordance with this invention therefore involves giving the material its final shape in the manner described above, or, if it is later to be machined, giving it roughly the shape of the final product. Once the cement has hardened, one of two alternative embodiments of this invention can be selected. The first embodiment simply alters the hardened matrix by infusing it with supercritical

CO

2 a dense gaseous-liquid phase of CO 2 The supercritical

CO

2 infusion may take place above or below the supercritical threshold temperature (31 0 C) of CO 2 so long as the CO 2 initially reached or exceeded the supercritical temperature threshold, and in one embodiment of the invention it takes place over a temperature range of between 20 and 310C.

The supercritical CO 2 infusion causes the hydroxides in the cement to convert to carbonates. It also alters the physical micro-structure of the material, simplifying, compacting and closely organizing what once was the calciumsilicate-hydrate phase into uniform, onyx-like grains with few pores and capillaries visible between them, even when viewed at a magnification of 10,000. The flat plates and needles in the crystal mass that would otherwise appear are entirely or very nearly absent.

Supercritical CO 2 at a pressure of approximately 100 atmospheres and a temperature ranging between 20 and 100C seems to produce the most uniform and evenly packed microstructure. The porosity and size of the material governs the amount of time required for complete infusion and carbonation to take place. More porous or cellular materials are infused and carbonated more rapidly than those that are denser.

Table 1 shows times and pressures for a variety of cements of varying densities to attain complete carbonation. The tests

I

.4 WO 96/40601 PCT/US96/08848 8 were conducted on samples which had a uniform thickness of about 2 cm.

Table 1 Typical C02 Cement Carbonation Parameters Density Pressure Temperature Duration in Cement type pounds per pounds/ in degrees minutes cubic foot square inch Celsius portland 20 990 8 1071 31 110 2055_ 26_ 180 33501 22 type-C fly ash 20 990 8 1071 28 110 1900 28 180 2300 32 The second embodiment of the present invention is similar to the first, except that the supercritical carbon dioxide (but not dense-phase CO 2 in addition to reacting with the hydroxides in the cement, acts as a transport medium or solvent to carry other dissolved or suspended (particulate) matter into a hardened hydraulic cement matrix. In this embodiment, the carbonation reaction occurs as above described, but it is part of a larger chemical and physical process. For example, zinc oxide or finely powdered (pulverulent) metallic zinc can be dissolved or suspended (as powder particles) in the supercritical CO 2 and be infused into the cement matrix to form such reaction products as hemimorphite and smithsonite. This reaction, only one of many possible, closes the capillaries and fills the micropores with reaction products. As a result, the cement matrix is rendered less permeable; for example, by water. The zinc infusion also increases the ductility of the cement.

To accomplish such an infusion of materials which are dissolvable or suspendable in supercritical C0 2 the supercritical CO 2 is first passed through a chamber containing the material and is then flowed into a chamber containing the hardened cement article. Materials which dissolve in CO 2 go into solution with it as the CO 2 passes through the chamber.

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WO 96/40601 PCT/US96/08848 9 Materials not dissolvable in CO 2 shall have been first pulverized into sufficiently small powder particles that they can flow with the supercritical CO 2 through the pores and capillaries of the cement matrix. They are appropriately mixed with; i.e. suspended in, the supercritical CO 2 before the cement matrix is exposed to it so that the entrained powder particles flow with the CO 2 through the pores and capillaries into the interior of the cement matrix.

In another embodiment of the invention the cement matrix is infused and carbonated with a plastic dissolved in the supercritical CO 2 This process is carried out as described in the preceding paragraph, except that the first chamber contains the plastic. Plastics used in this process are selected on a case-by-case basis and may include any one of the class of monomers, polymers or copolymers soluble in supercritical CO 2 Mixtures of plastics, metals, and/or metal salts and plastics and mixtures of metals and or metal salts may be infused, depending upon the final characteristics desired of the carbonated cement matrix.

By infusing metal into the cured cement matrix, it is also possible to change the electrical properties of the latter. For example, a desirable metal such as aluminum or copper can be pulverized to a powder particle size which is sufficiently small so that the particles can pass through pores and capillaries into and through the matrix. The metal powder is entrained in supercritical C0 2 the cement matrix is exposed to the C0 2 -metal powder mixture, and the CO 2 carries the powder particles with it into the cured cement matrix, where the powder particles are deposited. By heating the matrix above the melting temperature of the powdered metal, the latter is melted and forms interconnected electrically conductive layers on interior surfaces of the pores, voids, passages and capillaries of the cement matrix, thereby rendering the interior of the matrix electrically conductive.

According to another'embodiment of the invention, the supercritical carbon dioxide carbonation/infusion process can be used to quickly determine whether or not a cement matrix will carbonate at all. This is important in the

I,

WO 96/40601 PCT/US96/08848 construction industry, which relies upon cement alkalinity to protect steel reinforcing rod and mesh from corrosion. When added to cement pastes during the mixing process, hydroxypropyl methyl cellulose, an organic polymer, will prevent cement carbonation from taking place, and it is believed that there are other such materials which can be added to the wet cement mix. Until now it has not been possible to quickly determine whether or not such a material is present in the mix and whether or not the cement would, in fact, i:arbonate when exposed to naturally occurring CO 2 in the atmosphere, low-pressure CO 2 or supercritical CO 2 Infusion with supercritical CO 2 followed by either X-ray diffraction spectrometry or by exposing a small specimen of the matrix to phenolphthalein will quickly ascertain the extent, if any, to which the matrix of the specimen has carbonated. This provides a simple, fast test to determine if a material or materials have been added to the cement which will prevent carbonation of the cement matrix.

The range of articles and materials that may be created by means of supercritical CO 2 carbonation/infusion is quite broad. It includes many articles now made of opaque, rigid thermoplastics, metal or ceramics. It is expected that articles may be formed that are useful to the aerospace, automotive, manufacturing, construction, medical and petrochemical production industries. Because hardness, ductility, coefficient of expansion, electrical properties and many other factors may be controlled with this process, it is expected that items such as consumer goods, engine parts and even prosthetics can be manufactured from the class of materials made in accordance with the present invention.

Thus, the present invention makes possible cement products with characteristics which heretofore were unattainable, not only because of the severe limitations of the type and characteristics of fiber reinforcements and/or aggregates that could be mixed into the cement, but further because the present invention enables one to infuse materials into the cured cement which affect its chemical and/or physical properties. With carbonation and resultant pH WO 96/40601 PCT/US96/08848 11 neutralization, almost any fiber and/or aggregate can be mixed with the cement since the danger of decomposition of the reinforcing fibers is eliminated. Fibers such as glass can therefore be selected for their high tensile strength and others for flexibility (such as polyester) and they can be combined or blended to give the finished cement product characteristics combining a variety of properties. In addition, heretofore unattainable characteristics, such as internal electric conductivity of the cement matrix, are attainable with the present invention to further expand the uses of cement products. Since, moreover, cement products are relatively easy to initially form; e.g. by pouring the wet cement mixture into molds, new types of products at significantly reduced cost will become available.

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Claims

21. A method of improving a cured cement product, substantially as hereinbefore described.
22. A method of protecting alkali-intolerant matter in a cured cement product and changing characteristics of the cement product after curing, substantially as hereinbefore described.
23. A method of changing a characteristic of a cured cement product, substantially as hereinbefore described. Dated 5 December, 1997 Materials technology, Limited Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON r cc r C I I er a I e r I~:\LIBC102885:MCN IT II INTERNATIONAL SEARCH REPORT International application No. PCT/US96/08848 A. CLASSIFICATION OF SUBJECT MATTER IPC(6) :CO4B 40/00 US CL 106/638, 713, 738, 740: 264/61, 104, 333, DIG. 43 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) U.S. 106/638, 713, 738, 740; 264/61, 104, 333, DIG. 43 Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. A US,A, 5,358,676 (Jennings et al.) 25 October 1994 (See 1-20 col. 14 lines 1-29) A US,A, 5,307,876 (Cowan et al) 03 May 1994 (See claims 1- 1-20 18 in col. 16) A US,A, 4,069,063 (Baal) 17 January 1978 (See claims 1-11 1-20 in col. 13-14) Further documents are listed in the continuation of Box C. See patent family annex. S Special categories of cited documents: later document published after the international filing date or priority date and not in conlictwith the application butcited to understand the documentdefining the general state ofthe art which is not considered principle or theory underlying the invention to be of particular relevance rlier documet published o or afr the international ling dte "X docnent of particular relevance the claimed invention cannot be earlier document published on or after the internional filing dale considered novel or cannot be considered to involve an inventive step document which may throw doubts on priority claim(s) or which is when the document is taken alone cited to establish the publication date of another citation or other special reason (a specified) Y document of particular relevance; the claimed invention cannot be considered to involve an inventive step when the document is "0 document referring to an oral disclosure. use. exhibition or other combined with one or more other such documents. such combination means being obvious to a person skilled in the art document published prior to the international filing date but later than document member of the same patent family the priority date claimed Date of the actual completion of the international search Date of ailing of the international search report 01 JULY 1996 2 SEP1996 Name and mailing address of the ISA/US Authorized officer il Commissioner of Patents and Trademarks Box PCT PAUL MARCANTONI Washington, D.C. 20231 Facsimile No. (703) 305-3230 Telephone No. (703) 308-1196 Form PCT/ISA/210 (second sheet)(July 1992)* II -r II Ir I I